US4563532A - Process for the preparation of Δ4 -1,3,4-oxadiazolin-2-one compounds - Google Patents

Process for the preparation of Δ4 -1,3,4-oxadiazolin-2-one compounds Download PDF

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US4563532A
US4563532A US06/556,715 US55671583A US4563532A US 4563532 A US4563532 A US 4563532A US 55671583 A US55671583 A US 55671583A US 4563532 A US4563532 A US 4563532A
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Udo Eckstein
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • the present invention relates to a new process for the preparation of compounds of the formula ##STR3## wherein Y denotes a carbocyclic or heterocyclic aromatic radical,
  • R denotes hydrogen or R 1 ,
  • R 1 denotes an optionally substituted alkyl, aralkyl or aryl radical
  • n denotes 0 or 1
  • the rings A and B can carry further non-chromophoric substituents.
  • This heat-induced rearrangement proceeds surprisingly selectively, with migration of the radical R 1 from the oxygen to the adjacent, more nucleophilic nitrogen.
  • non-chromophoric substituents optionally present in the compounds of the formula I are the conventional non-chromophoric substituents of brightener chemistry, that is to say, for example, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, phenyl, phenoxy or Cl.
  • the rings A and B are preferably unsubstituted.
  • Suitable aromatic carbocyclic radicals Y are aryl radicals as defined below in more detail.
  • Suitable quasi-aromatic heterocyclic radicals Y are radicals of 5-membered or 6-membered mono-, di- or tri-nuclear heterocyclic compounds, such as, for example, those of the oxazole, imidazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,3-, 1,2,4- and 1,3,4-triazole, pyrimidine, 1,3,5-triazine, benzoxazole, benzothiazole, benzimidazole, naphthoxazole, benzo-s-triazole, naphtho-s-triazole, benzo(b)-furan, quinazoline or quinoxaline series, which are linked with the remainder of the molecule in a conventional manner.
  • Radicals from the benzoxazole, benzo(b)-furan, benzo-s-triazole, naphtho-s-triazole, 1,2,4- and 1,3,4-oxadiazole, 1,2,3-, 1,2,4- and 1,3,4-triazole and 1,3,5-triazine series are particularly preferred.
  • Suitable non-chromophoric substituents are R, OH, CN, OR, COR, SO 2 R, NHCOR, CONH 2 , NHSO 2 R, OCOR, COOR, COOH, NHR', SO 3 H and the like.
  • Alkyl is, in particular, C 1 -C 6 -alkyl, which can be substituted by hydroxyl, C 1 -C 4 -alkoxy, CN, carboxyl, C 1 -C 4 -alkoxycarbonyl, CONH 2 , chlorine or bromine, or trifluoromethyl.
  • Aryl is, in particular, phenyl which is optionally substituted by C 1 -C 4 -alkyl, trifluoromethyl, chlorine, bromine, carboxyl, cyano, C 1 -C 4 -alkoxycarbonyl or C 1 -C 4 -alkoxy.
  • Aralkyl is, in particular, phenyl-C 1 -C 4 -alkyl, which can be further substituted in the phenyl nucleus by chlorine, methyl or methoxy.
  • Y represents a 1,2,4-oxadiazole, 1,3,4-oxadiazole or 1,2,3-triazole radical, a benzoxazole radical which is optionally substituted by 1 or 2 C 1 -C 4 -alkyl groups, C 1 -C 4 -alkoxy, 1 or 2 chlorine atoms, benzyl, phenyl, cyclohexyl, C 1 -C 4 -alkylsulphonyl or C 1 -C 4 -alkoxycarbonyl, or a benzo(b)-furan, benzo-s-triazole, naphtho-triazole, 5-phenyl-1,3,4-oxadiazole, 5-phenyl-1,2,4-oxadiazole or 3-phenyl-1,2,4-oxadiazole radical, R represents hydrogen, C 1 -C 6 -alkyl which is optionally substituted by C 1 -C 4 -alkoxy, hydroxyl, chlorine or cyano
  • Y represents the radical of the formula ##STR8## and wherein n denotes 1,
  • R 2 denotes hydrogen, C 1 -C 4 -alkyl, cyclohexyl, C 1 -C 4 -alkoxy, chlorine, benzyl, phenyl, C 1 -C 4 -alkoxycarbonyl or C 1 -C 4 -alkylsulphonyl,
  • R 3 denotes hydrogen, C 1 -C 4 -alkyl, chlorine or C 1 -C 4 -alkoxy and
  • R 4 denotes hydrogen, C 1 -C 4 -alkyl or chlorine, is particularly preferred.
  • reaction of the tetrazole derivatives VII with the acid chlorides can be carried out in the temperature range from 0° to 120° C., preferably at 25°-90° C.
  • the reaction is advantageously carried out in inert solvents, for example ethers, such as dioxane, tetrahydrofuran or diisopropyl ether, and furthermore in hydrocarbons, such as toluene, xylene, chlorobenzene or 1,2-dichlorobenzene, or in formamides, such as dimethylformamide, dimethylacetamide or dimethylsulphoxide, preferably in the presence of acid acceptors, in particular tertiary organic bases, such as triethylamine, pyridine, dimethylaniline or hexahydrodimethylaniline.
  • inert solvents for example ethers, such as dioxane, tetrahydrofuran or diisopropyl ether, and furthermore in hydrocarbons, such as toluene, xylene, chlorobenzene or 1,2-dichlorobenzene, or in formamides, such as dimethylformamide, dimethylacetamide
  • the rearrangement of the compounds V into the compounds I can be achieved merely by heating the substance to beyond its melting point.
  • this reaction is advantageously carried out in the presence of a diluent, preferably a polar organic solvent, which is, needless to say, inert towards these substances.
  • suitable acids are mineral acids, such as hydrochloric acid and sulphuric acid, and sulphonic acids, such as benzenesulphonic acid and p-toluenesulphonic acid.
  • bases Either inorganic or organic compounds which are sufficiently soluble in the reaction mixture can be used as the bases.
  • Preferred bases are organic bases, such as, for example, triethylamine, N-methyl- or N-ethyl-piperidine, piperidine, pyrrolidine, 1,4-diazabicyclo[2,2,2]octane (DABCO), morpholine, N-methyl- or N-ethyl-morpholine and N-ethylpyrrolidine, or the like.
  • Suitable polar solvents are higher-boiling alcohols, such as n-butanol, tert.-butanol, glycol and diethylene glycol, glycol ethers, such as 2-methoxyethanol and 2-ethoxyethanol, nitriles, such as, for example, benzonitrile, and furthermore formamides, such as, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and phosphoric acid tris-dialkylamides, alkyl being, in particular, C 1 -C 4 -alkyl.
  • Non-polar solvents which may be mentioned are toluene, xylene, chlorobenzene and dichlorobenzene.
  • the reaction temperatures for the reaction according to the invention are between 100° and 250° C., preferably between 120° and 200° C.
  • the present invention furthermore relates to new compounds of the formula I, that is to say compounds of the formula I which are not described in the abovementioned German Offenlegungsschrift No. 2,833,470, wherein
  • R represents C 1 -C 4 -alkyl, C 2 -C 4 -chloroalkyl, C 2 -C 4 -hydroxyalkyl, cyanoethyl or C 1 -C 4 -alkoxy-C 2 -C 4 -alkyl.
  • These brighteners which are particularly readily accessible by the new process, are distinguished by improved technological properties compared with the nearest comparable known brighteners, such as, for example, a superior brightening effect on polyester fibres.
  • Y represents a benzoxazole radical, in particular a radical of the formula
  • the substance gives brilliant whitening effects on PES in the exhaustion-high temperature process and the thermosol process.
  • This substance also gives brilliant whitening effects on PES by the exhaustion-high temperature process and the thermosol process.
  • the compound gives outstanding whitening effects with very good fastness properties on PES.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Optical brighteners of the formula ##STR1## wherein Y denotes a carbocyclic or heterocyclic radical,
R denotes hydrogen or R1,
wherein
R1 is an optionally substituted alkyl, aralkyl or aryl radical, and
n denotes 0 or 1 and
the rings A and B can carry further substituents, are obtained in a simple manner by a process in which compounds of the formula ##STR2## are rearranged at elevated temperatures--if appropriate in the presence of acids.

Description

The present invention relates to a new process for the preparation of compounds of the formula ##STR3## wherein Y denotes a carbocyclic or heterocyclic aromatic radical,
R denotes hydrogen or R1,
R1 denotes an optionally substituted alkyl, aralkyl or aryl radical, and
n denotes 0 or 1 and
the rings A and B can carry further non-chromophoric substituents.
Some of the compounds of the formula I, which are useful optical brighteners, are known (compare German Offenlegungsschrift No. 2,833,470). According to this patent publication, these compounds are prepared either by reacting acid hydrazides of the formula ##STR4## with phosgene or chloroformates, or by condensing compounds of the formula ##STR5## with a compound of the formula ##STR6## wherein Z1 and Z2 are the conventional functional groups suitable for formation of --CH═CH-- bridges.
However, these processes have the disadvantages that they are not universally applicable (for example, compounds of the formula II in which R=alkyl cannot be prepared or can be prepared only with difficulty), or that the starting materials of the formulae III and IV can be obtained on an industrial scale only with a relatively high expenditure.
It has now been found that the compounds of the formula I can be prepared in a simple and economical manner by a process in which compounds of the formula ##STR7## are rearranged at temperatures of 100°-250° C.--if appropriate in the presence of acids.
This heat-induced rearrangement proceeds surprisingly selectively, with migration of the radical R1 from the oxygen to the adjacent, more nucleophilic nitrogen.
The non-chromophoric substituents optionally present in the compounds of the formula I are the conventional non-chromophoric substituents of brightener chemistry, that is to say, for example, C1 -C4 -alkyl, C1 -C4 -alkoxy, phenyl, phenoxy or Cl. However, the rings A and B are preferably unsubstituted.
Suitable aromatic carbocyclic radicals Y are aryl radicals as defined below in more detail.
Suitable quasi-aromatic heterocyclic radicals Y are radicals of 5-membered or 6-membered mono-, di- or tri-nuclear heterocyclic compounds, such as, for example, those of the oxazole, imidazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,3-, 1,2,4- and 1,3,4-triazole, pyrimidine, 1,3,5-triazine, benzoxazole, benzothiazole, benzimidazole, naphthoxazole, benzo-s-triazole, naphtho-s-triazole, benzo(b)-furan, quinazoline or quinoxaline series, which are linked with the remainder of the molecule in a conventional manner.
Radicals from the benzoxazole, benzo(b)-furan, benzo-s-triazole, naphtho-s-triazole, 1,2,4- and 1,3,4-oxadiazole, 1,2,3-, 1,2,4- and 1,3,4-triazole and 1,3,5-triazine series are particularly preferred.
Suitable non-chromophoric substituents are R, OH, CN, OR, COR, SO2 R, NHCOR, CONH2, NHSO2 R, OCOR, COOR, COOH, NHR', SO3 H and the like.
Alkyl is, in particular, C1 -C6 -alkyl, which can be substituted by hydroxyl, C1 -C4 -alkoxy, CN, carboxyl, C1 -C4 -alkoxycarbonyl, CONH2, chlorine or bromine, or trifluoromethyl.
Aryl is, in particular, phenyl which is optionally substituted by C1 -C4 -alkyl, trifluoromethyl, chlorine, bromine, carboxyl, cyano, C1 -C4 -alkoxycarbonyl or C1 -C4 -alkoxy.
Aralkyl is, in particular, phenyl-C1 -C4 -alkyl, which can be further substituted in the phenyl nucleus by chlorine, methyl or methoxy.
The preparation of compounds of the formula I wherein
Y represents a 1,2,4-oxadiazole, 1,3,4-oxadiazole or 1,2,3-triazole radical, a benzoxazole radical which is optionally substituted by 1 or 2 C1 -C4 -alkyl groups, C1 -C4 -alkoxy, 1 or 2 chlorine atoms, benzyl, phenyl, cyclohexyl, C1 -C4 -alkylsulphonyl or C1 -C4 -alkoxycarbonyl, or a benzo(b)-furan, benzo-s-triazole, naphtho-triazole, 5-phenyl-1,3,4-oxadiazole, 5-phenyl-1,2,4-oxadiazole or 3-phenyl-1,2,4-oxadiazole radical, R represents hydrogen, C1 -C6 -alkyl which is optionally substituted by C1 -C4 -alkoxy, hydroxyl, chlorine or cyano, or phenyl and n denotes 1,
is preferred.
The preparation of compounds of the formula I wherein
Y represents the radical of the formula ##STR8## and wherein n denotes 1,
R2 denotes hydrogen, C1 -C4 -alkyl, cyclohexyl, C1 -C4 -alkoxy, chlorine, benzyl, phenyl, C1 -C4 -alkoxycarbonyl or C1 -C4 -alkylsulphonyl,
R3 denotes hydrogen, C1 -C4 -alkyl, chlorine or C1 -C4 -alkoxy and
R4 denotes hydrogen, C1 -C4 -alkyl or chlorine, is particularly preferred.
The compounds of the formula V required as starting materials for the rearrangement according to the invention have not yet been described in the literature.
However, these compounds are easily obtained by reacting compounds of the formula ##STR9## with metal azides in polar organic solvents to give compounds of the formula ##STR10## and treating these with compounds of the formula ##STR11##
Only some of the compounds of the formula VI are known. They are obtained in a conventional manner, for example by reacting compounds of the formula ##STR12## wherein Z represents a grouping of the formula ##STR13## wherein R denotes C1 -C4 -alkyl, cyclohexyl or phenyl, with p-cyanobenzaldehyde (compare German Offenlegungsschrift No. 2,453,355, German Auslegeschrift No. 1,052,405 and Japanese Preliminary Published Application No. 49/85,378).
The reaction of the tetrazole derivatives VII with the acid chlorides can be carried out in the temperature range from 0° to 120° C., preferably at 25°-90° C.
The reaction is advantageously carried out in inert solvents, for example ethers, such as dioxane, tetrahydrofuran or diisopropyl ether, and furthermore in hydrocarbons, such as toluene, xylene, chlorobenzene or 1,2-dichlorobenzene, or in formamides, such as dimethylformamide, dimethylacetamide or dimethylsulphoxide, preferably in the presence of acid acceptors, in particular tertiary organic bases, such as triethylamine, pyridine, dimethylaniline or hexahydrodimethylaniline.
The rearrangement of the compounds V into the compounds I can be achieved merely by heating the substance to beyond its melting point. However, this reaction is advantageously carried out in the presence of a diluent, preferably a polar organic solvent, which is, needless to say, inert towards these substances.
Compounds of the formula I in which R1 denotes hydrogen are prepared by reacting compounds of the formula V in which R1 denotes alkyl with acids in polar organic solvents.
Examples of suitable acids are mineral acids, such as hydrochloric acid and sulphuric acid, and sulphonic acids, such as benzenesulphonic acid and p-toluenesulphonic acid.
The rearrangement can, however, also be carried out in non-polar solvents. Nevertheless, it is then advisable to add bases. Either inorganic or organic compounds which are sufficiently soluble in the reaction mixture can be used as the bases. Preferred bases are organic bases, such as, for example, triethylamine, N-methyl- or N-ethyl-piperidine, piperidine, pyrrolidine, 1,4-diazabicyclo[2,2,2]octane (DABCO), morpholine, N-methyl- or N-ethyl-morpholine and N-ethylpyrrolidine, or the like.
Suitable polar solvents are higher-boiling alcohols, such as n-butanol, tert.-butanol, glycol and diethylene glycol, glycol ethers, such as 2-methoxyethanol and 2-ethoxyethanol, nitriles, such as, for example, benzonitrile, and furthermore formamides, such as, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and phosphoric acid tris-dialkylamides, alkyl being, in particular, C1 -C4 -alkyl.
Non-polar solvents which may be mentioned are toluene, xylene, chlorobenzene and dichlorobenzene. The reaction temperatures for the reaction according to the invention are between 100° and 250° C., preferably between 120° and 200° C.
The present invention furthermore relates to new compounds of the formula I, that is to say compounds of the formula I which are not described in the abovementioned German Offenlegungsschrift No. 2,833,470, wherein
R represents C1 -C4 -alkyl, C2 -C4 -chloroalkyl, C2 -C4 -hydroxyalkyl, cyanoethyl or C1 -C4 -alkoxy-C2 -C4 -alkyl.
These brighteners, which are particularly readily accessible by the new process, are distinguished by improved technological properties compared with the nearest comparable known brighteners, such as, for example, a superior brightening effect on polyester fibres.
Particularly preferred compounds of the formula I are those in which
R has the abovementioned meaning and
Y represents a benzoxazole radical, in particular a radical of the formula
EXAMPLE 1
20.5 g (0.05 mol) of 5-ethoxy-1,3,4-oxadiazol-2-yl-stilbene of the formula ##STR15## are refluxed in 200 ml of dimethylformamide for 3 hours. After the mixture has been cooled to room temperature, the precipitated product is filtered off, washed with water and methanol and dried at 70° C. in vacuo. 18.5 g (90.4% of theory) of the compound of the formula ##STR16## are obtained, and can be recrystallised from dimethylacetamide. Melting point: 284°-85° C.; (absorption: λmax=366 nm; IR: νC═O =1777 cm-1).
______________________________________                                    
C.sub.25 H.sub.19 N.sub.3 O.sub.3                                         
             (409.5)    C %     H %   N %                                 
______________________________________                                    
           calculated                                                     
                    73.3    4.68    10.26                                 
           found    72.8    4.6     10.0                                  
______________________________________
The substance gives brilliant whitening effects on PES in the exhaustion-high temperature process and the thermosol process.
EXAMPLE 2
5.2 g (0.055 mol) of dimethylchlorocarbonate are added to a suspension of 18.3 g (0.05 mol) of 4-(benzoxazol-2-yl)-4'-(1,2,3,4-tetrazol-5-yl)-stilbene (formula 3) ##STR17## and 5.6 g (0.05 mol) of triethylamine in 200 ml of dimethylacetamide at room temperature. The mixture is then stirred at room temperature for 30 minutes and at 70° C. for 1 hour. The compound of the formula ##STR18## is thereby formed, and is not isolated.
A further 5.5 g of triethylamine are added to the mixture, which is then stirred at 130°-140° C. for 2 hours. After cooling to 20° C., the precipitate is filtered off, washed with water and methanol and dried in vacuo. 15.2 g (76.9% of theory) of light yellow crystals of the compound of the formula ##STR19## are thus obtained, and can be recrystallised from dimethylformamide. Melting point: 271°-73° C., (absorption: λmax=360 nm; IR: νCO =1776 cm-1). C24 H17 N3 O3, mass: m/e 395 (63%) M+.
This substance also gives brilliant whitening effects on PES by the exhaustion-high temperature process and the thermosol process.
EXAMPLE 3
Analogously to Example 1, rearrangement of 23 g (0.05 mol) of the compound of the formula ##STR20## in dimethylformamide gives 17.3 g (75.2% of theory) of a yellow crystalline powder of the compound of the formula ##STR21## which can be dissolved in and crystallised from dimethylformamide. Melting point: 270°-75° C., (absorption: λmax=376 nm, IR: νCO =1775 cm-1).
______________________________________                                    
C.sub.28 H.sub.21 N.sub.5 O.sub.2                                         
             (459.5)    C %     H %   N %                                 
______________________________________                                    
           calculated:                                                    
                    73.2    4.61    15.24                                 
           found:   72.9    4.7     15.5                                  
______________________________________
EXAMPLE 4
In the same manner as described in Example 1, 22.3 g (0.05 mol) of the methyl derivative (OCH3 instead of OC2 H5) of the formula (6) give 21.6 g (96.7% of theory) of light yellow crystals of the formula ##STR22## which can be recrystallised from dimethylformamide. Melting point: 274°-76° C., (absorption: λmax=376 nm, IR: νCO =1776 cm-1).
______________________________________                                    
C.sub.27 H.sub.19 N.sub.5 O.sub.2                                         
                    C %     H %     N %                                   
______________________________________                                    
           calculated:                                                    
                    72.8    4.3     15.72                                 
           found:   72.2    4.4     15.9                                  
______________________________________
The compound gives outstanding whitening effects with very good fastness properties on PES.
The following compounds are prepared in a manner analogous to that described in Examples 1-4:
______________________________________                                    
 ##STR23##                     (9)                                        
                                   Fluores-                               
                                   cence in                               
                                   dimethyl-                              
No.  Y                 Q           formamide                              
______________________________________                                    
 9.                                                                       
      ##STR24##        CH.sub.3    greenish- tinged violet                
10.                                                                       
      ##STR25##        C.sub.3 H.sub.7n                                   
                                   reddish- tinged blue                   
      ##STR26##        CH.sub.3    neutral blue                           
      ##STR27##        C.sub.4 H.sub.9n                                   
                                   blue- violet                           
      ##STR28##        CH.sub.3    neutral blue                           
      ##STR29##        CH.sub.2 CH.sub.2                                  
                                   neutral blue                           
      ##STR30##        CH.sub.2    reddish- tinged blue                   
      ##STR31##        CH.sub.2 CH.sub.2 OCH.sub.3                        
                                   blue                                   
      ##STR32##        C.sub.2 H.sub.5                                    
                                   reddish- tinged blue                   
      ##STR33##        CH.sub.3    neutral blue                           
      ##STR34##        C.sub.4 H.sub.9n                                   
                                   greenish tinged blue                   
______________________________________
EXAMPLE 5
50 g of concentrated hydrochloric acid are added dropwise to a suspension of 12.3 g (0.03 mol) of the compound of the formula (1) in 300 ml of dimethylformamide such that a temperature of 25°-30° C. is maintained. The mixture is stirred at 30° C. for 30 minutes and at 60° C. for 3 hours. It is then cooled to room temperature. The product is filtered off and washed with water and methanol. 7.8 g (68.2% of theory) of the compound of the formula ##STR35## are obtained in the form of light yellow crystals, which can be recrystallised from dimethylformamide. Melting point: >300° C., (absorption: λmax=366 nm, IR: νCO =1764 cm-1). C23 H15 N3 O3 (381.4), mass: m/e 381 (85%) M+.

Claims (2)

I claim:
1. A compound of the formula ##STR36## in which the rings A and B can carry further non-chromophoric substituents,
R is C1 -C4 -alkyl, C2 -C4 -chloroalkyl, C2 -C4 -hydroxyalkyl, cyanoethyl or C1 -C4 -methoxy-C2 -C4 -alkyl,
R2 is hydrogen, C1 -C4 -alkyl, cycloalkyl, C1 -C4 -alkoxy, chlorine, benzyl, phenyl, C1 -C4 -alkoxycarbonyl or C1 -C4 -alkylsulphonyl,
R3 is hydrogen, C1 -C4 -alkyl, chlorine or C1 -C4 -alkoxy, and
R4 is hydrogen, C1 -C4 -alkyl or chlorine.
2. A compound according to claim 1 of the formula ##STR37##
US06/556,715 1982-12-07 1983-11-30 Process for the preparation of Δ4 -1,3,4-oxadiazolin-2-one compounds Expired - Fee Related US4563532A (en)

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DE19823245202 DE3245202A1 (en) 1982-12-07 1982-12-07 METHOD FOR PRODUCING (ARROW UP) (DELTA) (ARROW UP) (ARROW UP) 4 (ARROW UP) -1,3,4-OXADIAZOLINE- (2) -ON COMPOUNDS

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246403A (en) * 1978-07-29 1981-01-20 Hoechst Aktiengesellschaft 1,3,4-Oxadiazolone-(2) compounds and process for their manufacture

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246403A (en) * 1978-07-29 1981-01-20 Hoechst Aktiengesellschaft 1,3,4-Oxadiazolone-(2) compounds and process for their manufacture

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